Reaction Environment Modification in Covalent Organic Frameworks for Catalytic Performance Enhancement

Herein, we show how the spatial environment in the functional pores of covalent organic frameworks (COFs) can be manipulated in order to exert control in catalysis. The underlying mechanism of this strategy relies on the placement of linear polymers in the pore channels that are anchored with catalytic species, analogous to outer‐sphere residue cooperativity within the active sites of enzymes. This approach benefits from the flexibility and enriched concentration of the functional moieties on the linear polymers, enabling the desired reaction environment in close proximity to the active sites, thereby impacting the reaction outcomes. Specifically, in the representative dehydration of fructose to produce 5‐hydroxymethylfurfural, dramatic activity and selectivity improvements have been achieved for the active center of sulfonic acid groups in COFs after encapsulation of polymeric solvent analogues 1‐methyl‐2‐pyrrolidinone and ionic liquid. Creating a solvation environment: The catalytic performance of sulfonic acid groups in covalent organic frameworks (COFs) can be greatly amplified by the introduction of polymeric solvent analogues, which create desired solvation environments through hydrogen‐bonding interactions. Improved activity and selectivity was demonstrated by the COF‐catalyzed dehydration of fructose to produce 5‐hydroxymethylfurfural.